Porous ceramic body to reduce emissions

ABSTRACT

A porous ceramic honeycomb body including a substrate of intersecting porous walls forming axial channels extending from a first end face to a second end face. An active portion of the walls include a zeolite catalyst disposed inside pores thereof and/or is comprised of an extruded zeolite and a three way catalyst (TWC) is disposed on wall surfaces of at least a portion of the active portion.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a continuation application of U.S. patent application Ser. No.15/738,434 filed on Dec. 20, 2017, which claims the benefit of priorityto International Patent Application Serial No. PCT/US2016/039710 filedon Jun. 28, 2016, and in turn claims the benefit of priority to U.S.Provisional Patent Application No. 62/185,874 filed on Jun. 29, 2015,the contents of each are relied upon and incorporated herein byreference in their entireties.

BACKGROUND Field

Exemplary embodiments of the present disclosure relate to porous ceramicbodies to reduce emissions, in particular porous ceramic bodies havingzeolite adsorber in wall and three way catalyst (TWC) on wall to reducehydrocarbons and volatile organic components (HC/VOC) emissions, anexhaust gas system incorporating the same, and methods of manufacturingthe same.

Discussion of the Background

After-treatment of exhaust gas from internal combustion engines may usecatalysts supported on high-surface area substrates and, in the case ofdiesel engines and some gasoline direct injection engines, a catalyzedor non-catalyzed filter for the removal of carbon soot particles. Porousceramic flow-through honeycomb substrates and wall-flow honeycombfilters may be used in these applications.

The above information disclosed in this Background section is only forenhancement of understanding of the background of the disclosure andtherefore it may contain information that does not form any part of theprior art nor what the prior art may suggest to a person of ordinaryskill in the art.

SUMMARY

Exemplary embodiments of the present disclosure provide a porous ceramicbody having zeolite disposed inside pores of walls of the porous ceramicbody and three-way catalyst (TWC) disposed on wall surfaces of theporous ceramic body.

Exemplary embodiments of the present disclosure also provide a method ofmanufacturing a porous ceramic body having zeolite disposed inside poresof walls of the porous ceramic body and three-way catalyst (TWC)disposed on the wall surfaces of the porous ceramic body.

Exemplary embodiments of the present disclosure also provide an exhaustgas system including the porous ceramic body having zeolite disposedinside pores thereof and TWC disposed on wall surfaces thereof.

Additional features of the disclosure will be set forth in thedescription which follows, and in part will be apparent from thedescription, or may be learned by practice of the disclosure.

An exemplary embodiment discloses a porous ceramic body comprising asubstrate of porous walls forming channels extending from a first endface to a second end face. The porous ceramic honeycomb body, comprisesan in wall zeolite catalyst disposed inside pores of a first portion ofthe walls, and a three way catalyst (TWC) disposed on wall surfaces ofthe first portion of the walls.

An exemplary embodiment also discloses a porous ceramic body comprisinga substrate of porous walls forming channels extending from a first endface to a second end face. The porous ceramic honeycomb body, comprisesa three way catalyst (TWC) disposed on wall surfaces of at least aportion of the walls, wherein the substrate comprises an extrudedzeolite catalyst.

An exemplary embodiment also discloses a method of manufacturing aceramic article. The method comprises extruding a zeolite catalystporous ceramic body and disposing three-way catalyst (TWC) on wallsurfaces of the walls of the porous ceramic body.

An exemplary embodiment also discloses a method of manufacturing aceramic article. The method comprises disposing zeolite catalyst insidepores in walls of a first portion of walls of a porous ceramic body; anddisposing three way catalyst (TWC) on wall surfaces of at least aportion of the first portion of the walls of the porous ceramic body.

An exemplary embodiment also discloses an exhaust gas system. Theexhaust gas system includes a housing having an inlet configured toaccept an exhaust gas stream to be purified, the housing having achamber configured to flow the exhaust gas stream through a porousceramic honeycomb body to purify the exhaust gas stream, and the housinghaving an outlet configured to emit the purified exhaust gas stream. Theporous ceramic honeycomb body disposed in the housing, comprises asubstrate of porous walls forming channels extending from a first endface to a second end face. The porous ceramic honeycomb body comprisesan in wall zeolite catalyst disposed inside pores of walls of a firstportion of the walls and a three way catalyst (TWC) disposed on wallsurfaces of at least a portion of the walls of the first portion ofwalls.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory and areintended to provide further explanation of the disclosure.

BRIEF DESCRIPTION OF THE FIGURES

The accompanying drawings, which are included to provide a furtherunderstanding of the disclosure and are incorporated in and constitute apart of this specification, illustrate exemplary embodiments of thedisclosure, and together with the description serve to explain theprinciples of the disclosure.

FIG. 1A shows a schematic perspective view of a honeycomb bodycomprising a skin on an outer periphery of a honeycomb core according toexemplary embodiments of the disclosure. FIG. 1B is a schematic crosssection through the honeycomb body of FIG. 1A according to theseexemplary embodiments of the disclosure. FIG. 1C is a schematic top viewof the honeycomb body of FIG. 1A according to these exemplaryembodiments of the disclosure.

FIG. 2 is a graphical plot of cold start engine out HC emissions in ppmcarbon over time in seconds during an Environmental Protection Agency(EPA) Federal Test Procedure-75 (FTP-75) cycle for a 3.8 L V6 engine ina vehicle.

FIG. 3 shows a graphical plot of cold start HC emissions in ppm carbonover time in seconds before a zeolite adsorber and after the zeoliteadsorber.

FIG. 4 shows schematic cross sections through walls of the conventionalsubstrate having about 34% porosity and the fast light-off, low mass,high porosity substrate having about 55% porosity.

FIG. 5 shows schematic cross sections through walls of a conventionalsubstrate having about 34% porosity, the fast light-off high porositylow mass substrate having about 55% porosity, and the fast light-offhigh porosity low mass substrate having zeolite disposed in the poresthereof according to exemplary embodiments of the disclosure.

FIG. 6 schematically illustrates a process that shows HC adsorption inzeolite in fast light-off high porosity low mass substrate pores duringcold start “CS” and desorption followed by oxidation over TWC on fastlight-off high porosity low mass substrate channel wall surface once thesubstrate has reached a higher temperature “HT” where TWC catalyticactivity occurs according to exemplary embodiments of the disclosure.

FIG. 7 illustrates a schematic cross section of a substrate having afirst portion of the cell channels having TWC disposed on the walls, butno zeolite disposed in pores of the walls of the first portion, and asecond portion having zeolite disposed in the pores of the walls and TWCdisposed on the walls according to these exemplary embodiments.

FIG. 8 shows a raw data plot of propylene concentration (ppm) 802 andinlet temperature (° C.) 804 as function of time (sec) for a comparativeexample having on wall TWC only.

FIG. 9 shows a raw data plot of propylene concentration (ppm) 902 andinlet temperature 904 (° C.) as a function of time (sec) for an examplehaving on wall TWC and zeolite disposed in wall according to exemplaryembodiments of the disclosure.

FIG. 10 provides an overlap view of the data from FIGS. 8 and 9 showingthe two light-off tests for TWC only in the comparative example andZSM-5 in pores and TWC on walls in the example of the exemplaryembodiment of the disclosure.

FIG. 11 shows exemplary embodiments of exhaust systems including aporous ceramic honeycomb body comprising a zeolite catalyst disposed inpores of the walls and a TWC disposed on surfaces of the walls.

FIG. 12 is a schematic of exhaust systems when a sorbing agent isdisposed in a porous ceramic honeycomb body and a TWC is disposed onsurfaces of the walls of another porous ceramic honeycomb body and thereis no porous ceramic honeycomb body comprising a sorbing agent disposedinside pores of at least a portion of the walls and a TWC disposed onwall surfaces of the portion of the walls.

DETAILED DESCRIPTION

The disclosure is described more fully hereinafter with reference to theaccompanying drawings, in which exemplary embodiments of the disclosureare shown. This disclosure may, however, be embodied in many differentforms and should not be construed as limited to the exemplaryembodiments set forth herein. Rather, these embodiments are provided sothat this disclosure is thorough, and will fully convey the scope of thedisclosure to those skilled in the art. In the drawings, the size andrelative sizes of layers and regions may be exaggerated for clarity.

It will be understood that when an element or layer is referred to asbeing “on” or “connected to” another element or layer, it can bedirectly on or directly connected to the other element or layer, orintervening elements or layers may be present. In contrast, when anelement or layer is referred to as being “directly on” or “directlyconnected to” another element or layer, there are no interveningelements or layers present. It will be understood that for the purposesof this disclosure, “at least one of X, Y, and Z” can be construed as Xonly, Y only, Z only, or any combination of two or more items X, Y, andZ (e.g., XYZ, XYY, YZ, ZZ).

In these exemplary embodiments, the disclosed article, and the disclosedmethod of making the article provide one or more advantageous featuresor aspects, including for example as discussed below. Features oraspects recited in any of the claims are generally applicable to allfacets of the disclosure. Any recited single or multiple feature oraspect in any one claim can be combined or permuted with any otherrecited feature or aspect in any other claim or claims.

While terms such as, top, bottom, side, upper, lower, vertical, andhorizontal are used, the disclosure is not so limited to these exemplaryembodiments. Instead, spatially relative terms, such as “top”, “bottom”,“horizontal”, “vertical”, “side”, “beneath”, “below”, “lower”, “above”,“upper” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the exemplary term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

“Include,” “includes,” or like terms means encompassing but not limitedto, that is, inclusive and not exclusive.

“About” modifying, for example, the quantity of an ingredient in acomposition, concentrations, volumes, process temperature, process time,yields, flow rates, pressures, viscosities, dimensions, and like values,and ranges thereof, employed in describing the embodiments of thedisclosure, refers to variation in the numerical quantity that canoccur, for example: through typical measuring and handling proceduresused for preparing materials, compositions, composites, concentrates, oruse formulations; through inadvertent error in these procedures; throughdifferences in the manufacture, source, or purity of starting materialsor ingredients used to carry out the methods; and like considerations.The term “about” also encompasses amounts that differ due to aging of acomposition or formulation with a particular initial concentration ormixture, and amounts that differ due to mixing or processing acomposition or formulation with a particular initial concentration ormixture.

The indefinite article “a” or “an” and its corresponding definitearticle “the” as used herein means at least one, or one or more, unlessspecified otherwise.

Abbreviations, which are well known to one of ordinary skill in the art,may be used (e.g., “h” or “hr” for hour or hours, “g” or “gm” forgram(s), “ml” for milliliters, and “RT” for room temperature, “nm” fornanometers, and like abbreviations).

Specific values disclosed for components, ingredients, additives, times,temperatures, pressures, and like aspects, and ranges thereof, are forillustration only; they do not exclude other defined values or othervalues within defined ranges. The apparatus, and methods of thedisclosure can include any value or any combination of the values,specific values, and more specific values described herein.

According to exemplary embodiments of this disclosure, an activematerial is disposed inside the pores of a substrate and a three-waycatalyst (TWC) is disposed on the surfaces of the channel walls of thesubstrate as will be described in more detail below. In an exemplaryembodiment, zeolite is disposed in the pores directly on the poresurfaces and the TWC is disposed directly on the wall surfaces.

An active material as used herein refers to material which can modify agaseous mixture, by reaction with the mixture components, by catalyticactivity, or by sorbing activity, or desorbing activity. The activematerial is preferably sorbing material and/or catalytic material. Thesorbing material or sorbing agents take up and hold substances by eitherabsorption or adsorption. In the present disclosure, a sorbing agent ispresent in the substrate pores to take up or remove selectedconstituents from a gaseous mixture under certain conditions. Theseconstituents can then desorb under certain conditions which arepredetermined. The term “sorbing material” or “sorbing agent” as used inthe present disclosure can refer to one or a plurality of sorbingagents. Adsorption is the taking up of molecules by physical or chemicalforces, termed respectively, physical or chemical adsorption. The term“adsorbing agent” according to the present disclosure refers to at leastone adsorbing agent. There can be more than one type of adsorbing agentin the pores of the substrate wall. The specific adsorbers can varydepending on the application. Catalyst material according to the presentdisclosure refers to a catalyst metal or catalyst metal oxide on asupport. Catalyst material includes also molecular sieves, such aszeolites when used in conversions such as, e.g., in cracking ofhydrocarbons or oxidation, etc.

Example adsorbing agents that are suited for removal of hydrocarbons arethose that adsorb at relatively low temperatures and desorb atrelatively high temperatures. For example, adsorbing agents that adsorbhydrocarbons at engine start-up temperatures which are typically lessthan about 150° C., and desorb at engine operating temperatures whichare typically greater than about 150° C. can be used. As disclosed inU.S. Pat. No. 5,260,035, hereby incorporated in its entirety as if fullyset forth herein, examples of adsorbing agents which can be used asdescribed herein without limitation are molecular sieves, activatedcarbon, transition aluminas, activated silicas, and combinations ofthese. Molecular sieves are crystalline substances having pores of sizesuitable for adsorbing molecules. Some example types of molecular sieveswithout limitation are carbon molecular sieves, zeolites,aluminophosphates, metallophosphates, silicoaluminophosphates, andcombinations of these. Carbon molecular sieves have well definedmicropores made out of carbon material.

In some embodiments, the active material can be without limitation, ametal exchanged or impregnated zeolite, for example, ZSM-5,beta-zeolites, mordenite, Y-zeolites, ultrastabilized Y-zeolites,aluminum phosphate zeolites, gmelinite, mazzite, offretite, ZSM-12,ZSM-18, Berryllophosphate-H, boggsite, SAPO-40, SAPO-41, combinationsthereof, and mixtures thereof.

The active material will be referred to herein as a zeolite forconvenience in the further detailed description. Zeolite, zeoliteadsorber, zeolite catalyst, zeolite-based catalyst, and the like areused herein interchangeably for convenience according to these exemplaryembodiments of the disclosure.

The TWC can include noble metal oxidation catalysts such as Pt, Rh,and/or Pd with a support such as alumina, ceria, titania, lanthana,zirconia etc. The oxidation catalyst serves to oxidize the hydrocarbonsmainly, to innocuous products as carbon dioxide and water, which aresuitable for passing into the atmosphere. The TWC can include a catalystfor conversion of NO_(x), CO, and hydrocarbons to innocuous products.For example, the TWC can include noble metal as e.g., Pt, Pd, Rh, orcombinations thereof on alumina, ceria, lanthana, zirconia, yttria, orcombinations thereof. The TWC suited to the practice of exemplaryembodiments of the present disclosure for stationary power plant exhaustconversion can include SCR catalyst for NOx reduction such aszeolite-based catalysts having transition metal or metals ion exchanged.Some example catalysts are Fe mordenite, Cu mordenite, ZSM-5 H⁺ form,and V₂O₅/TiO₂. The TWC suited to the practice of exemplary embodimentsof the present disclosure for auto exhaust conversion are, for example,Pt on ceria-alumina combined with Rh on zirconia. The Pt-ceria-aluminaand the Rh-zirconia can be combined and applied at once, as in a singlecoating or they can be applied in separate coatings. Another suitablecatalyst is Pt/Pd/Rh on gamma alumina with a rare earth oxide such asceria.

Improvements in engine efficiencies can lead to lower exhaust gastemperatures. Lower temperatures may lead to lower conversion of exhaustgas constituents on catalysts. Hybrid electric vehicles (HEVs), enginestarts and stops, other engine cycling, and the like can lead to morecold start HC emissions. As used herein, HC refers to hydrocarbons andvolatile organic components (HC/VOC). The disclosed zeolite disposedinside the pores of a substrate and a three-way catalyst (TWC) disposedon the surfaces of the channel walls of the substrate as describedherein can cost-effectively, efficiently, and passively reduce HCemissions under these types of conditions.

FIG. 1A shows a honeycomb body 100 including a plurality of intersectingwalls 110 that form mutually adjoining cell channels 112 extendingaxially in direction “A” between opposing end faces 114, 116. FIG. 1Bshows a schematic cross section through the honeycomb body 100 of FIG.1A. FIG. 1C shows a schematic top view of the honeycomb body 100 of FIG.1A. “Cell” is generally used herein when referring to intersecting wallsin cross section of the honeycomb body and “channel” is generally usedwhen referring to a cell extending between the end faces 114, 116. Celland channel may be used interchangeably as well as “cell channel”. Thetop face 114 refers to the first end face and the bottom face 116 refersto the second end face of the honeycomb body 100 positioned in FIG. 1A,otherwise the end faces are not limited by the orientation of thehoneycomb body 100. The top face 114 may be an inlet face and the bottomface 116 may be an outlet face of the honeycomb body 100 or the top face114 may be an outlet face and the bottom face 116 may be an inlet faceof the honeycomb body 100.

Cell density can be between about 100 and 900 cells per square inch(cpsi). Typical cell wall thicknesses can range from about 0.025 mm toabout 1.5 mm (about 1 to 60 mil). For example, honeycomb body 100geometries may be 400 cpsi with a wall thickness of about 8 mil (400/8)or with a wall thickness of about 6 mil (400/6). Other geometriesinclude, for example, 100/17, 200/12, 200/19, 270/19, 300/4, 600/4,400/4, 600/3, and 900/2. As used herein, honeycomb body 100 is intendedto include a generally honeycomb structure but is not strictly limitedto a square structure. For example, hexagonal, octagonal, triangular,rectangular or any other suitable cell shape may be used. Also, whilethe cross section of the depicted cellular honeycomb body 100 iscircular, it is not so limited, for example, the cross section can beelliptical, square, rectangular, other polygonal shape, or other desiredshape, and a combination thereof.

As used herein, porous ceramic body can refer to a honeycomb body, butis not so limited and can also refer to trough filters, radial flowfilters, and the like. Ceramic body compositions are not particularlylimited and can comprise major and minor amounts of cordierite,aluminum-titanate, mullite, β-spodumene, silicon carbide, zeolite andthe like, and combinations thereof. As a further example, the ceramichoneycomb body can comprise an extruded zeolite or other extrudedcatalyst.

The manufacture of porous ceramic honeycomb bodies may be accomplishedby the process of plasticizing ceramic powder batch mixtures, extrudingthe mixtures through honeycomb extrusion dies to form honeycombextrudate, and cutting, drying, and firing the extrudate to produceceramic honeycomb bodies of high strength and thermal durability havingchannels extending axially from a first end face to a second end face.As used herein a ceramic honeycomb body includes ceramic honeycombmonoliths and ceramic segmented honeycomb bodies.

A co-extruded or an after-applied exterior skin may form an outerperipheral surface extending axially from a first end face to a secondend face of the ceramic honeycomb bodies. Each channel of the honeycombbodies defined by intersecting walls (webs), whether monolithic orsegmented, can be plugged at an inlet face or an outlet face to producea filter. When some channels are left unplugged a partial filter can beproduced. The honeycomb body, whether monolithic or segmented, can becatalyzed to produce a substrate. A non-plugged honeycomb body isgenerally referred to herein as a substrate. The catalyzed substrate canhave an after applied catalyst or comprise an extruded catalyst.Further, filters and partial filters can be catalyzed to providemulti-functionality. The ceramic honeycomb bodies thus produced arewidely used as catalyst supports, membrane supports, as wall-flowfilters, as partial filters, and the like or as combinations thereof forcleaning fluids such as purifying engine exhausts.

When an internal combustion engine starts cold, a larger amount ofunburned hydrocarbons and carbon monoxide can be emitted in the firstminutes or less than when the internal combustion engine is warm. Alsothe larger amount of unburned hydrocarbons and carbon monoxide can passthrough a cold catalyst without converting to CO₂, and H₂O. Closecoupling the catalyst to the engine, for example, positioned within lessthan six inches (15.24 cm) of the engine exhaust manifold can reduce theun-burnt hydrocarbons (HC) and carbon monoxide (CO) by more quicklywarming the catalyst. Nevertheless, cold start emissions can account forgreater than 80% of the total emissions, for example, for a vehicleduring a drive cycle. FIG. 2 illustrates the engine out cold start HCemissions in ppm carbon 202 (dashed line) and the engine out exhausttemperature 204 (solid line) over time in seconds during anEnvironmental Protection Agency (EPA) Federal Test Procedure-75 (FTP-75)cycle for a 3.8 L V6 engine in a vehicle.

After the catalyst is warmed up, after about 20-30 seconds, most of theemissions (HC, CO, NOx) get converted to CO₂, H₂O, and N₂ by the warmcatalyst. To reduce catalyst warming time, lower mass close coupledsubstrates having high porosity and significantly lower density can beutilized. For example, the density can be about 30% less thanconventional porous ceramic honeycomb substrates having similar celldensity and wall thickness. For example, when cordierite density istaken as about 2.5 g/cm³, a 400/6 conventional porous ceramic honeycombsubstrate of cordierite can have a density of about 0.41 g/cm³ withabout 27 percent porosity (% P), whereas the 400/6 low mass porousceramic honeycomb substrate of cordierite can have a density of about0.31 g/cm³ with about 45% P, a density of about 0.25 g/cm³ with about55% P, or a density of about 0.20 g/cm³ with about 65% P. For example, a600/3 conventional porous ceramic honeycomb substrate of cordierite canhave a density of about 0.26 g/cm³ with about 27% P, whereas the 600/3low mass porous ceramic honeycomb substrate of cordierite can have adensity of about 0.20 g/cm³ with about 45% P, a density of about 0.16g/cm³ with about 55% P, or a density of about 0.12 g/cm³ with porosityof 65%.

For another example, when the material is an aluminum titanatecomposite, for example, about 70% aluminum titanate phase having adensity of about 3.7 g/cm³ and about 30% strontium feldspar phase havinga density of about 3.0 g/cm³ thus giving the composite density of about3.5 g/cm³, a 400/6 conventional porous ceramic honeycomb substrate ofaluminum titanate composite can have a density of about 0.57 g/cm³ withabout 27 porosity (% P), whereas the 400/6 low mass porous ceramichoneycomb substrate of aluminum titanate composite can have a density ofabout 0.43 g/cm³ with about 45% P, a density of about 0.35 g/cm³ withabout 55% P, or a density of about 0.28 g/cm³ with about 65% P. Forexample, a 600/3 conventional porous ceramic honeycomb substrate ofaluminum titanate composite can have a density of about 0.36 g/cm³ withabout 27% P, whereas the 600/3 low mass porous ceramic honeycombsubstrate of aluminum titanate composite can have a density of about0.27 g/cm³ with about 45% P, a density of about 0.22 g/cm³ with about55% P, or a density of about 0.17 g/cm³ with porosity of 65%.

Having faster light-off compared to standard substrates can be providedby the lower mass substrates. These low mass high porosity substratescan reduce engine out emissions. Testing has shown that there is nearlya 10% HC reduction using such a low mass high porosity substrate for aclose coupled catalyst.

Another approach to reducing the cold start HC release includesproviding zeolites to adsorb this large amount of HC. The low mass highporosity substrates provide pores that can accommodate zeolites disposedtherein. Zeolites adsorb HC at low temperature and zeolites laterrelease the HC at higher temperature to allow conversion to CO₂ and H₂Oby the warm catalyst. FIG. 3 shows that a substantial amount of HC isadsorbed over the zeolite catalyst. Curve 302 (dashed line) indicates HCbefore the zeolite adsorber and curve 304 (dot-dashed line) indicates HCafter the zeolite adsorber. Curve 306 (solid line) indicates exhausttemperature before the zeolite adsorber and curve 308 (double solidline) indicates exhaust temperature after the zeolite adsorber.

For example, zeolite technology and zeolite coating can be used fordiesel oxidation catalysts (DOC) in diesel vehicles. In such anapplication, it was found that zeolites adsorb >80% HC from cold startemissions. Thus, it is beneficial to take advantage of the properties ofzeolites to adsorb HC to further reduce emissions during cold start andduring normal driving cycle on fast light-off, low mass, high porositysubstrates. The DOC catalysts can have a porosity of less than about40%, for example, less than about 35%, a porosity of about 10% to about30%, or even a porosity of about 15% to about 20%. The DOC catalysts canhave a median pore size of about 7-10 μm, and the density of thesubstrate can be about 0.19-0.35 gm/cm³ at a 400/4 geometry.

The fast light-off, low mass, high porosity substrates, can have aporosity of greater than about 40%, for example, greater than about 45%,greater than about 50% and even greater than about 55%. For example,high porosity low mass substrates can have a porosity between about 50%and 70%. The fast light-off high porosity low mass substrate can have amass of about 190 gm for an about 4 inch (5.1 cm) diameter×about 4 inch(5.1 cm) length, about 600/3 geometry with about 55% porosity. Bycomparison a conventional substrate sample with about 34% porosity has amass of about 290 gm for about the same size and geometry.

FIG. 4 shows schematic cross sections through walls of the conventionalsubstrate having about 34% porosity and the fast light-off high porositylow mass substrate having about 55% porosity. The higher mass, lowerporosity wall 402 is represented by a darker shade than the lower mass,higher porosity wall 404.

Exemplary embodiments of the disclosure are directed to a porous ceramicbody having zeolite disposed in pores of walls of the porous ceramicbody and three-way catalyst (TWC) disposed on wall surfaces of theporous ceramic body. In these exemplary embodiments this conceptincludes zeolite coated exclusively inside the pores of the substrateand TWC coated on the wall surfaces of the channels. Zeolite coatedinside the pores of the substrate is referred to herein as “in wall” andTWC coated on the wall surfaces is referred to herein as “on wall”.Optionally, when the porous ceramic body is an extruded zeolite,additional zeolite can be coated inside the pores of the substrate, butneed not be.

FIG. 5 shows schematic cross sections through walls of the conventionalsubstrate 502 having about 34% porosity, the high porosity low masssubstrate 504 having about 55% porosity, and the high porosity low masssubstrate 504 having zeolite 506 disposed in the pores 508 thereofindicated by a cross hatch fill. The higher mass, lower porosity wall502 can have a larger median pore size than the lower mass, higherporosity wall 504. For example, the lower mass, higher porosity wall 504can have a median pore size of about 7 to 10 μm. TWC 512 is coated onthe channel walls 502, 504, and zeolite 506 is disposed in the pores 508of the lower mass, higher porosity wall 504 illustrated in FIG. 5insert. “G” represents the gas flow through the channels of the porousceramic substrate, including, for example, HC, CO, NOx, O₂, etc.

Fast light-off high porosity low mass substrate 504 with zeolite 506disposed in the pores 508 and TWC 512 disposed on the walls will adsorbHC in the zeolite 506 during cold start of the cycle. As the TWC 512catalyst gets heated these adsorbed HC desorb from zeolite 506, which isalso heated, to get oxidized over the TWC 512 on the surface of thewalls. There will be some temperature gradient between the surface TWC512 and zeolites 506 in the pores 508 due to wall thickness and mass.This process is schematically illustrated in FIG. 6 that shows HCadsorption 602 in zeolite 506 in fast light-off high porosity low masssubstrate pores 508 during cold start “CS” and desorption 604 followedby oxidation 606 over TWC 512 on high porosity low mass substrate 504channel wall surface once the substrate has reached a higher temperature“HT” where TWC catalytic activity occurs. “CS” refers to coldercondition during adsorption 602, while “HT” represents hotter substrateand catalyst during desorption 604 and oxidation cycle 606.

In these exemplary embodiments, the zeolite 506 disposed in the pores508 can adsorb HC during cold start at and below a certain temperatureand desorb HC above the certain temperature, and the TWC 512 disposed onthe walls can decompose at least a portion of the desorbed HC in atemperature range having an upper limit above the certain temperature.For example, the certain temperature is a catalyst light-off temperaturebetween about 100° C. and about 300° C., for example, a catalystlight-off temperature between about 100° C. and about 250° C.

According to these exemplary embodiments of the disclosure, zeolite canbe in the pores and TWC can be disposed on the walls throughout theentire length of the cell channels of the low mass, high porositysubstrate, alternatively zeolite can be disposed only in pores of aportion of the cell channels of the low mass, high porosity substrate.For example, a center portion extending axially and spaced apart from atleast one end face may have zeolite disposed in pores of the channelwalls. For example, a center portion extending axially and spaced apartfrom an input end face may have zeolite disposed in pores of the channelwalls. In these instances, the TWC can be disposed on the portion havingthe zeolite disposed in the pores as well as the portion extending tothe at least one end face. Having no zeolite disposed in the channels atan input end portion can provide low mass density allowing the substrateand TWC in such a portion to heat up more rapidly than if zeolite waspresent in the pores. Having no zeolite disposed in the channels at anoutlet end portion can provide, for example, cost savings of catalystmaterial.

According to these exemplary embodiments of the disclosure, zeolite canbe disposed only in pores of a first portion of the cell channels of thelow mass, high porosity substrate and TWC can be disposed on at least aportion of the walls of the first portion of the cell channels of thelow mass, high porosity substrate. For example, in some of theseexemplary embodiments, the first portion of the walls can extend atleast partially from the first end face to the second end face. Forexample, in some of these exemplary embodiments, the first portion ofthe walls can be spaced apart from the first end face by a firstdistance, and the first end face can be an inlet side of the porousceramic honeycomb body. For example, in some of these exemplaryembodiments, a second portion of the walls can extend from the first endface to the first portion of the walls. For example, in some of theseexemplary embodiments, the walls extending between the first end faceand the first portion of the walls can have a lower density than thefirst portion of the walls. For example, in some of these exemplaryembodiments, the first portion of the walls can be spaced apart from thesecond end face by a second distance. For example, in some of theseexemplary embodiments, the first distance and the second distance can besubstantially the same or different. For example, the first distanceand/or the second distance can be about 5% of the length of the lowmass, high porosity substrate, for example, about 10%, about 15%, about20%, about 25%, about 30%, about 40%, or even about 50% of the length ofthe low mass, high porosity substrate, for example, between about 10%and 50% of the length of the low mass, high porosity substrate dependingon the catalyst light off temperature and HC adsorption capacity. Forexample, in some of these exemplary embodiments, a third portion of thewalls extends from the second end face to the first portion of thewalls.

The second and third portions can have no zeolite disposed inside poresof the walls and have TWC disposed on at least a portion of the secondportion and/or the third portion.

FIG. 7 illustrates a schematic cross section of a substrate 700 havingan input end face 702 and an output end face 704, a first portion 706 ofthe cell channels having zeolite disposed in the pores of the walls andsecond and third portions 708, 710 of the cell channels having TWCdisposed on the walls, but no zeolite disposed in pores of the walls ofthe second and/or third portions 708, 710. The first portion 706 havingzeolite disposed in the pores of the walls can have TWC disposed on thewalls according to these exemplary embodiments of the disclosure. Suchan arrangement provides an advantage of keeping the mass density low inthe beginning, end or other desired section of the high porosity lowmass substrate. The first portion 706, second portion 708, and/or thirdportion 710 design can be varied as needed to optimize HC adsorption anddesorption cycles and manage the desired heat cycles.

EXAMPLES

Exemplary embodiments of the disclosure are further described below withrespect to certain exemplary and specific embodiments thereof, which areillustrative only and not intended to be limiting.

A high porosity, low mass honeycomb body was coated with zeolite slurrycomprising ZSM-5 and AL-20. The zeolite slurry was disposed only in thewall pores. After drying, the high porosity, low mass honeycomb bodyhaving zeolite disposed in wall was coated with three-way catalyst (TWC)as a layer on the channel wall surfaces. The sample was fired and testedfor hydrocarbon (HC) adsorption and desorption/oxidation using C₃H₆ inaccordance with exemplary embodiments of the disclosure. C₃H₆ wasadsorbed under CS conditions and a significant portion was oxidizedduring heating cycle (HT). A comparative sample was coated with TWC onlyand then similarly fired and tested for hydrocarbon (HC) adsorption anddesorption/oxidation.

The high porosity, low mass honeycomb body substrate having dimensionsof about 1 inch (2.54 cm) diameter by about 3 inch (7.62 cm) length wascoated with TWC (about 0.1 g/cc) using a vacuum coating process, withoutzeolite. An about 1 inch (2.5 cm) diameter by about 1 inch (2.4 cm)length sample of this comparative catalyzed sample was tested in a lightoff bench test with about 400 ppm propylene, 5000 ppm carbon monoxide,500 ppm nitric oxide, 14% CO₂, 10% steam (H₂O), 1700 ppm hydrogen (H₂),balance nitrogen with space velocity of 90,000 ch/hr (ch refers tovolumetric changes so that ch/hr refers to volumetric changes per hourherein) and a total flow of about 17.4 liters/min, using Fouriertransform infrared spectroscopy (FTIR) detector. FIG. 8 shows a raw dataplot of propylene concentration (ppm) 802, and catalyst on substrateinlet temperature (° C.) 804 and outlet temperature (° C.) 806 asfunction of time (sec) for the sample having on wall TWC. There was noremoval of propylene before the catalyst heats up as shown in Region“CS”. Propylene was oxidized at about 280 sec and the concentrationdecreased to less than about 50 ppm as shown in region “HT”. The spikesin the propylene curve between about 0 and 100 sec and between about 100and 200 sec are instrument anomalies caused by changing scale.

The same high porosity, low mass honeycomb body substrate havingdimensions of about 1 inch (2.5 cm) diameter by about 3 inch (7.6 cm)length was coated with ZSM-5 zeolite at about 0.1 g/cc loading in thepores followed by coating the same TWC as used in the comparativeexample at about 0.1 g/cc loading on the channel wall surfaces accordingto exemplary embodiments of the disclosure as described herein. A sampleof about 1 inch (2.4 cm) diameter by about 1 inch (2.6 cm) length sampleof this exemplary catalyzed sample was tested in a light off bench testwith 400 ppm propylene, 5000 ppm carbon monoxide, 500 ppm nitric oxide,14% CO₂, H₂O, 10% steam, 1700 ppm hydrogen, balance nitrogen with spacevelocity of 90,000 ch/hr and 17.9 liter/min total flow, using Fouriertransform infrared spectroscopy (FTIR) detector as explained above forthe comparative example. FIG. 9 shows a raw data plot of propyleneconcentration (ppm) 902, and inlet temperature (° C.) 904 and outlettemperature (° C.) 910 as a function of time (sec) for the examplehaving on wall TWC and zeolite disposed in wall according to exemplaryembodiments of the disclosure. Referring to FIGS. 8 and 9, it can beseen that the propylene concentration 902 is much lower at the beginningof the test from about 15 second start time in the exemplary embodimentof the disclosure indicating significant adsorption of propylene inZSM-5 zeolite coated in the high porosity, low mass honeycomb bodysubstrate pores. As the temperature heats up indicated by curve 904 andthe catalyst gets heated the propylene concentration 902 decreases tozero indicating the oxidation reaction over TWC. In cold start regionCS, HC adsorption occurred as indicated by box 906 (See FIG. 10 areabetween curves 902 and 802). As the TWC catalyst and zeolite were heatedHC desorption and decomposition occurred as indicated by ellipse 908(See FIG. 10 shaded area between curves 902 and 802). This exampleexothermic reaction shows the adsorption of propylene (HC) on zeoliteand desorption and oxidation during heat up cycle over TWC on thesurface.

FIG. 10 provides an overlap view of the data from FIGS. 8 and 9 showingthe two light-off tests for TWC only in the comparative example andZSM-5 in pores and TWC on walls in the example of the exemplaryembodiment of the disclosure as described herein. The Figure comparingthe two examples shows that nearly more than about 60% of the propyleneis adsorbed and a small fraction (<10%) of the propylene desorbed andthe rest of the hydrocarbon oxidized to CO₂. These examples clearlydemonstrate the advantage of coating zeolite in pores of the fastlight-off, high porosity, low mass honeycomb body substrate having TWCcoated on wall to provide adsorption at low temperature followed bydesorption and oxidation of adsorbed propylene over the TWC at hightemperature.

Zeolites in automotive catalysts have been found by the applicant toadsorb a broad range of HC, including, for example, from C₃ to C₁₀ HCchains, alkanes, alkenes, aromatics, and the like. The zeolites havebeen found to remain stable and reliable for greater than about 100,000miles (about 161,000 km). Combining the zeolites with the fastlight-off, high porosity, low mass honeycomb body substrate deposited inthe pores thereof and the TWC deposited on the walls demonstrates theconcepts of the exemplary embodiments of the disclosure.

While not wishing to be bound by theory, the path of the HC to beadsorbed by the zeolite disposed in pores of the walls can be very shortleading to rapid adsorption because the walls of the fast light-off,high porosity, low mass honeycomb body substrate are thin. As usedherein, path simply refers to the path the gas takes to penetrate thesubstrate walls. In addition, the path of the desorbed HC to the TWCcatalyst is also short for the same reason leading to efficientadsorption at low temperature and desorption and oxidation at hightemperature. The TWC disposed on wall tends to heat to catalytictemperature prior to mass in wall. Thus, HC desorbed when the bulk ofthe wall heats up can be readily oxidized by the heated catalyst leadingto efficient adsorption at low temperature and desorption and oxidationat high temperature. Furthermore, the thin porous wall heats more easilythan a thicker, less porous wall such that the zeolite is efficientlyutilized to release adsorbed HC to be oxidized.

In an exemplary embodiment of a diesel oxidation catalyst (DOC) having alower porosity (% P), for example, in a range from 10% P to 35% P,according to this disclosure, zeolite can be disposed in pores in thewall of the DOC and TWC can be disposed on wall as described herein. Inthe instance of a DOC, the zeolite can adsorb HC when the engine cycleruns at a cool temperature followed by desorption and oxidation of HC asdescribed and demonstrated above when the engine cycle runs at a hottemperature.

In some of these exemplary embodiments, an exhaust system for cleaning afluid such as engine exhaust, can comprise the low mass substrate havinghigh porosity or lower porosity, with zeolite disposed inside pores inwall and TWC disposed on wall of the substrate as described herein. Thesubstrate may be disposed in a housing, which may be deployed in a fluidtreatment system such as an exhaust system. The housing may be referredto as a can, and the process of disposing the ceramic honeycomb body inthe can may be referred to as canning.

FIG. 11 shows exemplary embodiments of exhaust systems including aporous ceramic honeycomb body comprising a zeolite catalyst disposed inpores of the walls and a TWC disposed on surfaces of the walls. Thesystem 3 according to some of these embodiments can include an engine 5or other source of fluid stream “G”, such as exhaust gas stream, to bepurified, a housing 7 having a chamber 8 to mount the substrate 9, afilter 11, and an outlet pipe 13, such as a tail pipe or exhaust stack.The housing 7 can have an inlet 12 to direct the gas stream G into thechamber 8 and through the channels of the substrate 9 disposed in thehousing chamber 8 whereby the gas stream is purified as described abovewith regard to some of the exemplary embodiments. The purified gasstream G1 can exit the housing 7 through an outlet 14 and be filtered asit passes through walls of a through-wall filter 11 having inlet andoutlet channels sealed with plugs 20 at respective outlet and inlet endsproviding a purified and filtered gas stream emission from tail pipe 13.The filter 11 can be a diesel particulate filter or a gas particulatefilter and can be upstream or downstream of the substrate 9 according tosome of these exemplary embodiments. Furthermore, additional componentsof the exhaust system may include, for example, a selective catalyticreduction (SCR) catalyst and other compatible components.

In system 21, according to some of these exemplary embodiments, thesubstrate is located further from the engine 10 and without aparticulate filter 11 such that purified gas stream G1 can directly exitthe tail pipe 13. That is, in system 3, the substrate may be closecoupled to the engine 5 to provide fast light-off as described aboveaccording to various exemplary embodiments of the disclosure. Likewise,while the substrate 9 may not be close-coupled to the engine 10 in thesystem 21, the system 21 may nevertheless include a filter, SCRcatalyst, and the like, and combinations thereof. When the substrate 9has a low mass density inlet portion as described above with referenceto FIG. 7, a sorbing agent to adsorb cold start and/or cold cycleemission constituents and desorb the emission constituents at atemperature near or above a three way catalyst (TWC) light-offtemperature, and such a TWC to decompose the desorbed emissionconstituents, according to some of the exemplary embodiments describedherein, then the substrate may need not be so closely coupled to theengine, providing more flexibility in system design where space islimited, while still providing full drive cycle emissions below targetregulations.

Furthermore, components not having the sorbing agent and TWC disposedaccording to these exemplary embodiments can lead to inefficiencies. Forexample, as shown in FIG. 12, a sorbing agent 33 disposed closer to anengine 35 than a TWC 37 would adsorb emission constituents in exhaustgas stream G, but the TWC 37 would be delayed in heating up, even,perhaps, reaching light off temperature after the sorbing agent desorbsthe constituents at a desorbing temperature. On the other hand, a TWC 37closer to the engine 35 would heat up faster, but would not be able todecompose the desorbed constituents. Further, a TWC 37 closer to theengine and an additional TWC 39 further from the engine than the sorbingagent 33 would add additional components and weight and requireadditional space.

It will be apparent to those skilled in the art that variousmodifications and variations can be made in the present disclosurewithout departing from the spirit or scope of the disclosure. Thus, itis intended that the appended claims cover the modifications andvariations of this disclosure provided they come within the scope of theappended claims and their equivalents.

1. A method of manufacturing a ceramic article, comprising: disposingzeolite catalyst inside pores in walls of a first portion of walls of aporous ceramic body; and disposing three way catalyst (TWC) on wallsurfaces of at least a portion of the first portion of the walls of theporous ceramic body.
 2. The method of claim 1, wherein the TWC comprisesat least one of hydrocarbon oxidation, CO oxidation, and NOx reductioncatalysts.
 3. The method of claim 1, wherein the walls of the porousceramic body define axial channels extending from a first end face to asecond end face of the porous ceramic body, and the first portion of thewalls extends at least partially from the first end face to the secondend face.
 4. The method of claim 1, wherein the first portion of thewalls is spaced apart from the first end face by a second portion of thewalls.
 5. The method of claim 4, wherein the second portion of the wallsis substantially free of zeolite catalyst inside pores of the walls. 6.The method of claim 4, wherein the second portion of the walls has alower density than the first portion of the walls.
 7. The method ofclaim 4, wherein the first portion of the walls is spaced apart from thesecond end face by a third portion of the walls.
 8. The method of claim7, wherein the third portion of the walls is substantially free ofzeolite catalyst inside pores of the walls.
 9. The method of claim 7,wherein the second portion of the walls and the third portion of thewalls are each substantially free of zeolite catalyst inside pores ofthe walls.
 10. A porous ceramic honeycomb body, comprising: a substrateof porous walls forming channels extending from a first end face to asecond end face; and a three way catalyst (TWC) disposed on wallsurfaces of at least a portion of the walls, wherein the substratecomprises an extruded zeolite catalyst.
 11. A method of manufacturing aceramic article, comprising: extruding a zeolite catalyst porous ceramicbody; and disposing three way catalyst (TWC) on wall surfaces of thewalls of the porous ceramic body.
 12. An exhaust system, comprising: aporous ceramic honeycomb body, comprising: a substrate of porous wallsforming channels extending from a first end face to a second end face;an in wall zeolite catalyst disposed inside pores of a first portion ofthe walls; and a three way catalyst (TWC) disposed on wall surfaces ofat least a portion of the walls of the first portion of walls; and ahousing, comprising: an inlet configured to accept an exhaust gas streamto be purified, an outlet configured to emit purified exhaust gasstream, and a chamber between the inlet and outlet configured to directthe exhaust gas stream to be purified into the first end face of thesubstrate, wherein the substrate is disposed in the chamber.
 13. Thesystem of claim 12, further comprising an engine configured to generateand output an exhaust gas stream to the inlet of the housing.
 14. Thesystem of claim 12, wherein the substrate mounted in the chamber of thehousing is close coupled to the engine.
 15. The system of claim 12,further comprising at least one of a filter and a selective catalyticreduction (SCR) catalyst configured to purify the exhaust gas stream.